A General Method for the Synthesis of t-Butyl Esters

aniline.1 2. The method has now ... recent investigations,3·4 but the detailsfor their synthesis were not ... 73-74 at 25. 70 ... 113° at 12 mm. At ...
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Vol. 65

986

NOTES A General Method for the Synthesis of t-Butyl Esters BY B. ABRAMOVITCH, J. C. SHIVERS,B. E. HUDSONAND C. R. HAWSER

There are several good methods for the preparation of t-butyl acetate from t-butyl alcohol. The one described in "Organic Syntheses"' employs acetyl chloride and magnesium. We prefer the method using acetyl chloride and dimethylaniline.2 The method has now been developed and extended to the preparation of various t-butyl esters. Certain of these esters have been used in recent i n v e ~ t i g ~ t i o nbut s , ~ the ~ ~ details for their synthesis were not giveii. The general procedure is described below. One mole each of dry t-butyl alcohol and dry dimethylaniline and 150-200 cc. of dry ether were placed in a flask equipped with a reflux condenser, mercury-sealed mechanical stirrer, and a dropping funnel. One mole of the appropriate acid chloride was added slowly from the dropping funnel. If refliing became too vigorous the flask was immersed in an ice-bath. The reaction mixture (containing a precipitate of dimethylaniline hydrochloride) was finally heated on the water-bath for one to two hours and allowed to stand for several hours (except in the experiment with bromoacetyl bromide; this was added a t 0' and the mixture allowed to stand a t room teinperature for a few hours). The mixture was stirred with water until the solid material disTABLEI YIELDSOF I-BUTYLESTERS Acid chloride used Acetyl chloride Propionyl chloride i-Butyryl chloride i-Valeryl chloride Bromoacetyl bromide

I-Butyl ester obtained Acetate' Propionate' Isobutyrate' I sovalerateb a-Bromoacetate'

Cinnnmyl chloride

CinnumateC

Yield,

B. p., " C . 98.0-98.6 118-118.5 127.0-128.3 154.0-156.0 73-74 at 25 mm. 144 at 8 mm.

%

63-76 63 71 33 70 58

Anul. Calcd. for CsHlsOn: C, 66.62; H, 11.18. Found: C, 66.23; H,11.09. * Anel. Calcd. for CpH1802: C, 68.22; H, 11.47. Found: C, 68.05; H, 11.33. Anul. Calcd. for ClaHlsOg: C , 7G.44;H, 7.90. Found: C, 76.04; H. 7.90. (1) Spassow, "Orgnnic Syntheses," 40,21 (1040). (2) See Norris and Rigby, THISJOURNAL,54, 2097 (1932).

(3) Abramovitch and Hauser. ibid., 64,2274 (1042) (4) Hauser. Ahramovitch nnd Adorns. ihid , 64, 2714 (1042)

solved. The ether layer was separated aiid extracted with portions of 10% sulfuric acid until the extract did not become cloudy when made alkaline. The ether solution was dried with sodium sulfate followed by Drierite and the solvent distilled. The residue was fractionated. The yields and analytical data for the t-butyl esters are given in Table I. DEPARTMENT OF CHEMISTRY DUKEUNIVERSITY DURHAM, NORTH CAROLINA RECEIVED MARCH 8, 1943

By-product 1,3-Butylene Glycol BY J. B . CLOKEAND R . M. WOLFF~

The usual method fur the preparation of 1,3butylene glycol consists in the reduction of aldol. Some time ago 1)r. Emil R. Stein of the Shawinigan Chemicals, Ltd., informed one of us that he had prepared this glycol by the alkaline saponification of one of their by-products. This byproduct, consisting mainly of the acetate of 1,3butylene glycol, was obtained to the extent of 4 to 6% in the production of ethyl acetate by the Tischtschenko reaction, in particular by the action of aluminum butoxide on acetaldehyde. In the following procedure, the crude 1,3butylene ester is alcoholized in the presence of hydrochloric acid and the liberated glycol is then separated by distillation. Methyl Alcoholysis.-A mixture of 1500 cc. of the by-product ester residue, kindly supplied by Dr. Stein, 2560 cc. of methanol and 9 cc. of concentrated hydrochloric acid was heated in a flask attached to a jacketed twentyfour bulb Snyder column2 and a stillhead which was regu!;lted to give a high r d u x ratio. The distillation was conducted slowly until the methyl alcoholysis was complete and the methyl acetate and methyl alcohol had been removed. The 1,3-butylene glycol (594 cc.) was obtained by the fractionation of the residue under diminished pressure. The compound boiled at 113" at 12 mm. At atmospheric pressure, a fraction was collected of b. p. 206-207 ', dz0, 1.005, n% 1.435, which values correspond closely with the recorded data for 1,3-butylene glycol. Ethyl Alcoholysis.-A mixture of 1500 cc. of by-product butylene ester, 2890 cc. of ethyl alcohol and 9 cc. of con(1) This note has been constructed from a thesis submitted by Robert M. Wolff to the Faculty of the Reneselaer Polytechnic Institute in partial fulfillment of the requirements for the degree of Bachelor of Chemicnl Engineering, June 10, 1941. (2) A smaller uod \impler roliimn rnav he used with equally satisi 4 r t o r i rt..;ult\